Methylamine → 3-Bromo-N-methyl-5-nitrobenzamide

HRID 1592343Notes

Reaction equation

HRID 1592343 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:8]=[C:9]([N+:11]([O-:13])=[O:12])[CH:10]=1)[C:5](O)=[O:6].C(Cl)(=O)C(Cl)=O.[CH3:20][NH2:21]>C(Cl)Cl.CN(C=O)C.C1COCC1>[Br:1][C:2]1[CH:3]=[C:4]([CH:8]=[C:9]([N+:11]([O-:13])=[O:12])[CH:10]=1)[C:5]([NH:21][CH3:20])=[O:6]

Participants

7

Reactant 3

HCID 6329MethylamineHCID 65578Oxalyl chlorideHCID 2393363-Bromo-5-nitrobenzoic acid

Product 1

HCID 222526863-Bromo-N-methyl-5-nitrobenzamide

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideCatalystHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 3-bromo-5-nitrobenzoic acid (17.7 g) and oxalyl chloride (2 equiv.) in 250 mL of anhydrous CH2Cl2 was added a few drops of DMF, and the mixture was stirred for 2 hrs at room temperature. It was concentrated in vacuo, then reconcentrated in vacuo twice from 400 mL of toluene to remove excess oxalyl chloride. The residue was dissolved in 100 mL of anhydrous THF. In a separated flask methylamine (3 equiv.) was dissolved in 100 ml of anhydrous THF and cooled to 0° C. Then the acid chloride solution was added dropwise, causing a white solid to precipitate. The mixture was allowed to stir at room temperature for 16 hrs, and the solids were removed by filtration. The filtrate was concentrated in vacuo to provide a white solid, which was triturated with diethyl ether, collected by filtration to yield 3-bromo-N-methyl-5-nitrobenzamide. NMR (300 MHz, DMSO-d6) δ 9.92 (m, 1H), 8.64 (s, 1H), 8.53 (s, 1H), 8.43 (s, 1H), 2.81 (d, 3H, J=7 Hz).

Workup

  1. concentrationIt was concentrated in vacuo
  2. customto remove excess oxalyl chloride
  3. dissolutionThe residue was dissolved in 100 mL of anhydrous THF
  4. temperaturecooled to 0° C
  5. customto precipitate
  6. stirringto stir at room temperature for 16 hrs
  7. customthe solids were removed by filtration
  8. concentrationThe filtrate was concentrated in vacuo
  9. customto provide a white solid, which
  10. customwas triturated with diethyl ether
  11. filtrationcollected by filtration

Sources & evidence

ORD record
ord-c9e5b8f7e9fa4856adbb1fb24f4766b6
Source dataset
uspto-grants-2007_11
Patent number
US07291744B2

Reaction notes

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